Heterocyclic compounds containing sulfur and nitrogen in the ring



Patented Jan. 6, 1953 UNITED STATES OFFICE HETEROCYCLIC COM'POUNDSCONTAINI NG SULFUR AND NITROGEN IN THE 'RIN G Sidney Melamed,Philadelphia, and Willard J. V Croxall, Bryn Athyn, Pa., assignors toRohm & 'Haas'Company, Philadelphia, Pa., 3. corporation of Delaware NoDrawing. Application December'l, 1950, Serial No; 198,724

wherein Ads in its preferred form an alkylene chain of two to threecarbon atoms,-R; is an 'alkyl, -aralkyl, or cycloalkyl group, 'and=X isa sulfur linkage which together with the nitrogen atoms and the alkylenegroup forms a heterocycle. The group represented by X may take the formof -Sz-- including S--, -SO, or SO2, where :c is a small integer.

The compounds which are defined by the above structural formula areprepared by reacting together an alkylenediamine of the formulaRNHA-NHR, where A is a 1,2- or a 1,3-alkylene group, with a sulfurchloride including sulfur dichloride, thionyl chloride, or sulfurylchloride or the comparable sulfur bromides. The reaction is bestefiected in thepresence of an inert organic solvent, such as naphtha,benzene,'t-oluene, petroleum ether, ethyl ether, isopro'pyl ether, orthe like. Thereaction is carried out in general below 50 C. and ispreferably undertaken at ate'mpera- 'ture between and 30 C.

The reaction proper involves 'one mole of the acceptor present therefor.This is mosteffe'ctiv'ely done by using an excess of the diamine. Hence,in the practical accomplishment of the reaction two moles of diamine areused per moleof sulfur acid halide. In some cases, however, where theproduct is not sensitive to strong alkalies, other alkaline agents maybe used in place of excess of diamine. This is a procedure which may inparticular be successfully used when sulfuryl chloride is one of thereactants, in which case astrong alkali, such as sodium hydroxide orpotassium hydroxide, may be used as acceptor for the hydrogen halide.There may similarly be used a strongly basic tertiary amine as anacceptor; such as pyridine.

The N,N-disubstituted' diamines" are 1,2- or 1,3-alk'ylenediamines"which have as the N,N'- substituents' alkyl; aralkyl, or cycloalkylgroups.

In particular the N;N'-disubstituted Lz ethylenediamines and. theN,N-fdisubs'tituted I,2-'or 1,3-

' propylenediamines are of interest; although other alkylenediamines 7such as 2,3- butylene or 1,3- hexylene-, or the-like diamines may alsobeused. The size of the 'nitrogen"'substltuents may vary (c1. zed-2'43)from the methyl group 'to octadecyl. groups or dodecylbenzylgroupsor-the like, a practicalupper limit'for theN-groups being 18 or 19carbon atoms. Typical alkyl groups include I methyl,

ethyl, propyl,*butyl,*hexyl, octyl, nonyl,-decyl, "dodecyl, hexadecyl,and octaclecyl groups and other alkyl groupsin'their various isomericforms. As typical of the aralkylgroups there ma be mentioned benzyl,methylbenzyl, butylbenzyl,

Further" details of the preparation of typical 1 compounds of thisinvention are given in the fol- -lo'w'ing illustrative examples. flPar-ts: given are by weight unless otherwise designated.

"Example 1 A solution of 68' parts ofsulfuryl chloride in parts ofpetroleum ether was added slowly to 88 parts ofN,N-dimethylethylenediamine in 300 parts of-petroleum ether at 0-5 C.The reaction was stirred forfive hours and the solvent was decanted'ofi.The residual .solid was extracted with several portions of hot ether.The combined extracts were concentrated, and the residual syrup wasallowed to crystallize. Recrystallization from a mixture of benzene andnaphtha gave 25 parts of a hygroscopic, white solid, which correspondedin composition to 2,5-dimethyl-1,2,5-thiadiazolidine-Ll-dioxide. This,product contained by analysis 18.67% of nitrogen and 21.33% of sulfur.Corresponding theoretical values are 18.72% and 21.03% respectively.

This compoundhas the "structural formula mo- 031 new N-cm s 2 Exam le? Acooled solution of 112 partsof*N,N'-dicyclo- 'hexylethylenediamine'in400' parts. of naphtha was treated slowly with stirring with 34 partsof sulfuryl chloride. The mixture was stirred at room temperaturefo'rthreehours and'filtered. Concentration "of the filtrate-gave 7-partsof solid product. An additional '21- parts was'isolated by extractingthe' original precipitate with two portions of ether and evaporating theether. This represents a combined yield of 40% The product whenrecrystallized ,from ethanol has a melting point of S P-96C. Itcorrespondsin'composition to2,5-dicyclohexyl-1,2,5-thiadiazolidine-1,1-diox- Example 3 A solution of112 parts of lI,l l'-dicyclohexylethylenediamine in 240 parts of naphthawas treated dropwise while the mixture was cooled and stirred with 34parts of sulfur monochloride. The reaction mixture was stirred for fivehours at room temperature and then filtered. Concentration of thefiltrate gave 21 parts of very sticky oil as product, which correspondedin composition to 3.6-dicyclohexyl-tetrahydro-1,2,3,6-dithiadiazine. Theproduct contained by analysis 9.5% of nitrogen and 21.3% of sulfur(theory 9.78% and 22.38% respectively).

Example 4 A solution of 149 parts of N,N-di-(2-ethylhexyl)trimethylenediamine in 400 parts of naphtha was cooled to 3 C. andtreated while it was stirred and cooled with 26 parts of sulfurdichloride at 3-10 C. over a half hour period. The mixture was stirredat room temperature for one and one-half hours, diluted with 750 partsof naphtha and filtered. The solid filtered ofi was washed with twoportions of naphtha, each of about 750 parts, and dried to give 101parts. The

theoretical yield of diamine dihydrochloride is 93 4.

parts. The combined filtrates were concentrated. and the product wasisolated as a viscous residue of 65 parts, an 80% yield of2,6di-(2-ethylhexyl)perhydro-1,2,6-thiadiazine. This product containedby analysis 8.1% of nitrogen and 10.8% of sulfur (theory 8.53% and 9.76%respectively).

This compound may be represented by the formula CH2 H2o oH: 04119011OIL-I l I\ICHZCHC4HQ c lia. s c2115 Example 5 A solution of 119 parts ofN,N'-di-2-(ethylhexyl) trimethylenediamine in 750 parts of naphtha wascooled in an ice bath and treated with 24 parts of thionyl chloride. Themixture was stirred for an additional five hours at room temperature andfiltered. The solid was washed with naphtha and dried to give 68 parts(91%) of the theoretical amine dihydrochloride. The filtrate wasconcentrated in vacuo and the product isolated as a viscous concentratein 73% yield (50 parts). It was 2,6-di-(2-ethylhexyl)perhydro-1,2,6-thiadiazine-1-oXide, which contained by analysis 7.9% of nitrogenand 8.1% of sulfur (theory 8.14% and 9.3% respectively).

The formula for this compound is 01H; SO CZ n 4 Example 5 Sulfurylchloride, 27 parts, was added dropwise to a naphtha solution of 119parts of l-l,N-di- (Z-ethylhexyl)trirnethylenediamine at i-l0 C. inminutes. The mixture was warmed to C. and stirred for an additional fivehours and filtered. The precipitate was washed with naphtha and dried togive 60 parts or 61% of the theoretical dihydrochloride. The filtratewas washed with a mixture of ethanol and dilute aqueous hydrochloricacid and then with 69% aqueous ethanol until neutral. Removal of thesolvent and concentration in vacuo allowed the isolation of the productas a concentrate, *9 parts being thus obtained of 2,6-di-(2-ethyih.yl)perhydro- 1.2,6-thiadiazine-1,1-dioxide. It contained by analysis7.4% of nitrogen and 8.7% of sulfur (theory 7 9% and 8.9% respectively).

Example 7 where the CQHll) group is 3,5,5-trin1ethylhexyl.

Example 8 Sulfur monochloride, parts. was added slowly to a solution of210 parts of N,l-l-di-(3,5,5-trimethylhexyl)ethylenediamine in 250 partsof naphtha at 5-10 C. The mixture was stirred for an additional threehours at 25 C. and then treated with 30 parts of a filter aid andfiltered. The filtrate was stripped in vacuo and the product wasisolated as a viscous red oil in an amount of 68 parts in a yield. Anadditional 16 parts was obtained by re-extracting the solid precipitate,thus increasing the yield to 68% of 3.6-di- (3,5,5trimethylhexyl)tetrahydro 1.2.3.6 dithiadiazine. This contained byanalysis 7.0% of nitrogen and 17.3% of sulfur (theory 7.47% and 17.1%respectively).

A probable structure for this compound is HZC CH2 Colin- Q IL'COTimwhere Cal-I19 represents the 3,5.5-trimethylhexyl group.

Example 9 A solution of 210 parts of N ,N -di-(3.5,5-trimethylhexyl)ethylenediamine in 350 parts of petroleum ether was treated at 5 C. with39.7 parts of thionyl chloride. When the addition was complete, thecooling bath was removed and the mixture was stirred continuously andallowed to become warm from the heat of reaction. The mixture thickenedconsiderably, a solid formed, and the mix was allowed to stand for 12hours. Filteraid was added and the solid removed by filtration.Concentration of the filtrate gave 86 parts, 72%. of viscous, orange oilas product. This correrepa r-r229 sponded in composition.to..2,5sdi-(3,5,5-trimethylhexyl) -1,2,5 thiadiazo1idine 1-oxide. Ityielded the following analyticaldata:* nitrogen-'l.5 %-and sulfur 8.2(theory 7.8 and 8':92%respectively). *Example 'ia Awell-stirredmixture'of 38 parts of-N,N*-dinonylethylenediamine, "20 'parts ofpowdered "po- 'tassium hydroxide,"'and 140*parts of-anhydrous 'ether'wascooled in an 'ice'bathand treated drop- "wise with16.2*parts*of*sulfuryl chloride. *The mixture was stirredfor'three'hours, diluted with benzene, and poured into ice-water withstirring. The organic layer was separatedand washedwith ice water, with"dilute "hydrochloric "acid in ethanol, and with aqueous ethanol untilit was neutral. The organic layer was concentrated in vacuo to yield asa viscous oil 2,5-di-(3,5,5-trimethylhexyl) 1,2,5thiadiazolidine-Ll-dioxide. This contained by analysis 7.3% of nitrogenand 7.9% of sulfur (theory 7.49% and 8.56% respectively) Example 11 Asolution of 111 parts of N-N'-didodecylethylenediamine in 250 parts ofether was treated dropwise with sulfur dichloride, 14 parts, while thereaction mixture was stirred and cooled. The mixture was then stirredfor eight hours and filtered. The filtrate was concentrated to give 43parts of a dark, semi-solid product, 2,5-didodecyl-1,2,5thiadiazolidine.This contained by analysis 6.2% of nitrogen and 7.6% of sulfur (theory6.58% and 7.52% respectively).

Example 12 A solution of 56.4 parts of N,N'-dioctadecylethylenediaminein 500 parts of naphtha was treated with 13.5 parts of sulfuryl chlorideand stirred for five hours. There was then added 16 parts of a 50%sodium hydroxide solution and stirring was continued for an hour. Layerswere allowed to form and were separated. The oil layer was treated withwater and layers again were formed and separated. The solvent wasevaporated and the residue was stripped by being heated to 150 C./1 mm.The residue corresponded in composition to2,5-dioctadecyl-perhydro-1,2,5-thiadazine-1,1-dioxide.

Example 13 A solution of 51 parts of N,N-dibenzyl-1,2 propylenediaminein 400 parts of toluene was cooled to C. and. treated with 12 parts ofthionyl chloride. The mixture was stirred for four hours at roomtemperature and then filtered. The solid was rinsed with petroleum etherand combined with the filtrate, which was then concentrated underreduced pressure. A brown oil was obtained which corresponded incomposition to 2,5-dibenzy1-3-methyl-1,2,5-thiadiazolidine-1- oxide,containing 9.2% of nitrogen and 10.5% of sulfur (9.3% and 10.7% beingthe respective theoretical values). This compound has the structure OH:H: C-- CH Co s C r- CHzCuHs The compounds of this invention havepesticidal properties and, hence, find use in insecticidal andfungicidal compositions in which they may be diluted with liquid or withfinely divided solid. Some typical test data follow.

-'A "spray containing 2,'6 di(- 2 ethylhexyl)perhydro-1,2,6-thiadiazineat a dilution-of 1'i 400was applied to plants infested with aphids andwith red spiders. A control 1 of 97% was obtained against the former andch98 against the latter. In standard fungitoxicity tests" there was a100% inhibition of germination of spores of Sclerotima fructzcola and:Macrospor-ium .rsarcinaejorme :at 0.0005% and at 0.01% respectively.I-n;tests determine the tenacity .ot thecompoundunder a water sprayvalues of over 16 minutestwerevobtained, the tenacity value being thetime which a cellulose nitrate coated plate dried with test compound canbewater -washed without permitting germination of sporesttoiaensue.

In tests with 2,6edi (2-ethylhexyl)perhydro- 1,2,6-thiadiazine-1-oxidethere was 100% inhibitionof germination ofsporesi'ofbothofthaabovewherein A is an alkylene chain of two to three carbon atoms, X is asulfur linkage selected from the class consisting of Sx--, SO-, and-SO2- groups wherein a: is an integer having a value of one to two, andthe designated alkyl groups contain not over 18 carbon atoms each.

2. As a new chemical substance, a compound of the formula CHa-CH whereinthe alkyl groups contain not over 18 carbon atoms each.

3. As a new chemical substance, a compound of the formula CH:CHI

alkylN N-alkyl wherein the alkyl groups contain not over 18 carbon atomseach.

4. As a new chemical substance, 2. compound of the formula CHa-CH:

alk l-N N-alkyl wherein the alkyl groups contain not over 18 carbonatoms each.

v the formula 5. As a new chemical substance, a compound of CH2 CH2 5alkyl. I 1 \'a1ky1 s 2 Number wherein the alkyl groups contain not over18 carbon atoms each.

10 14 6. As a new chemical substance, a compound 4 2,473,0.-2 of theformula 1 CH2 E Number 15 49,191 alkyl-N N-alkyl wherein the alkylgroups contain not over 18 carbon atoms each.

SIDNEY MELAMED. 20

WILLARD J. CROXALL.

REFERENCES CITED 0112 The following references are of record in the fileof this patent:

UNITED STATES PATENTS Name Date Lincoln et a1. Aug. 11, 1942 Walter Nov.16, 1948 Oberright Jan. 11, 1949 Walter June 14, 1949 FOREIGN PATENTSCountry Date Germany Oct. 4, 1899

1. AS NEW CHEMICAL SUBSTANCES, COMPOUNDS OF THE FORMULA